CN102702835A - Low-VOC (Volatile Organic Compound) water-based coating additive - Google Patents
Low-VOC (Volatile Organic Compound) water-based coating additive Download PDFInfo
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- CN102702835A CN102702835A CN2012101800217A CN201210180021A CN102702835A CN 102702835 A CN102702835 A CN 102702835A CN 2012101800217 A CN2012101800217 A CN 2012101800217A CN 201210180021 A CN201210180021 A CN 201210180021A CN 102702835 A CN102702835 A CN 102702835A
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Abstract
The invention relates to an additive, which comprises: (a) carboxylic acid, (b) amine, (c) alcohol and (d) organic silicon, wherein the molar ratio of a to b to c to d is (2.0-3.0):(11.5-14):(45-90):(2-10). The invention further relates to a water-based coating additive containing the additive. The water-based coating additive comprises: (a) film forming resin, (b) an effective amount of carboxylic acid, (c) amine, (d) alcohol and (e) organic silicon. The coating has the additional advantage of environmental ideality as well as excellent wetting performance. The VOC (Volatile Organic Compound) content of the coating is generally less than or equal to about 2.0 pounds solvent/gallon (except water), and is an environment-friendly coating.
Description
Technical field
The present invention relates to be used for the additive of low-VOC aqueous coating.More particularly, these additives comprise carboxylic acid, amine, pure and mild organosilicon; When being used for aqueous based systems, these additives reduce surface tension.
Background technology
Generally coating is applied over the inside of metal food and beverage container, to prevent the metallic surface of content contacting container.With some food, especially the acid product contact can cause the metal vessel corrosion.This corrosion has caused the pollution of Foods or drinks product and the deterioration of outward appearance and taste.
The interior supercoat that is applied over metal tin generally is the coating with low extractable matter, to avoid the pollution of content.Coating should be flawless basically also, and should have the high patience to various food and drink.Also need be to the good adhesion of metallic surface and good wetting, cover metal fully and in baking and shaping operation process, protect metal guaranteeing.Yet obtain the foaming that the required high temperature of fast curing speed has usually caused coating.Foaming is general to be taken place when solidification value surpasses the boiling point of water, the covering that can cause the incomplete of jar inside or weaken.
In addition, after the jar manufacturing, aqueous coating must tolerate the strict relatively temperature and pressure requirement that jar is stood in food processing process, and is in case the jar of filling provides necessary corrosion-resistant level.
VOC is a volatile organic compounds, and HUMAN HEALTH is had tremendous influence.When the VOC in the room reaches finite concentration; In short period of time people can feel headache, feel sick, vomiting, weak etc.; Can have a convulsion, go into a coma when serious, and can hurt people's liver, kidney, brain and neural system, cause serious consequences such as hypomnesis.
The coating that uses in the decoration design for residence process is one of main source of indoor VOC.So each state all limits the VOC content in the decorating and renovating materials such as coating.
Limits of harmful substances in the coating National Standard GB18582-2001 indoor decorating material interior wall coating " in the definition of VOC content be: " total volatile content is reduced moisture content in the coating, is content of volatile organic compound in the coating." generally speaking, contained VOC is few more in the material, it is just slight more to the harm of human body.Requirement to VOC content in the interior wall coating in the coating GB is: must not be higher than every liter 200 gram.
Developed countries is very strict to the restriction of VOC content in the coating.With European Union, one type of (inferior light class) coating must not be higher than every liter 30 gram, and two types (the light class is arranged) must not be higher than every liter 200 gram; And at home, the aqueous inner wall paint environmental labelling product authentication requesting of the up-to-date issue of State Environmental Protection Administration regulation, VOC must not be higher than every liter 100 gram; " the indoor decorating coating safety and Health quality evalution rule " that Beijing formulates is must be below every liter 125 gram to the requirement of VOC.
CN100351327C discloses a kind of low-VOC aqueous coating with excellent wetting ability.Said composition comprises film-forming resin and the interpolation that contains carboxylic acid, amine and alcohol.The invention also discloses preparation and use these method for compositions and additive itself.But additive processing characteristics according to the invention is relatively poor, is unfavorable for conventional the use.
Summary of the invention
The present invention relates to the additive of low-VOC aqueous coating, comprise carboxylic acid and amine, pure and mild organosilicon.This additive can be incorporated in the liquid waterborne coating (comprising painted water-borne coatings).These coating also are within the scope of the invention.
Additive of the present invention is used to reduce the surface tension of the water-borne coatings that has added them.This has caused the improvement " wetting " of the coating on the metallic surface." wetting " is to be used to refer to coating in the art, and especially water-based coating does not have the term of the ability of defective basically with the continuous film covering substrates.The use that comprises the compsn of these additives has caused the covering very completely of the metallic surface of jar; Especially distinguish on the first coat (wash coat) of splash in jar inside with at the disc (bead) of jar, they are to be difficult to obtain the place that sufficient coating covers in history.Better the coating fraction of coverage is with better erosion resistance is relevant.Importantly, additive of the present invention has strengthened the performance of coating, and coating is had no negative impact.Be difficult to find the additive of the performance that does not have the disadvantageous effect coating, because the requirement of application of paints is very harsh; In the coating of jar, use hot setting very fast, and jar has stood very high temperature and pressure after filling.The jar that scribbles the coating that contains additive of the present invention also provides excellent enamel paint grading (enamel rater) performance, and it has guaranteed that jar is applied basically.The attendant advantages of compsn of the present invention is that they have low volatile organic solvent content (VOC).Therefore their use is useful on environment.
Detailed description of the present invention
The present invention relates to comprise carboxylic acid, amine, pure and mild organosilyl additive.
Carboxylic acid can have from the about 2 any carbonatomss to about 18 carbon atoms.Very clear, the carboxylic acid with 2-7 carbon atom generally is unpleasant, and therefore their uses in some applications possibly be unfavorable.Have 8-18 carbon especially the carboxylic acid of 10 ~ 15 carbon therefore generally be more suitable for, especially for the application of food cans.This carboxylic acid can be obtained by animal or plant fat or oil, or in animal or plant fat or oil, contains (that is lipid acid).The instance of the acid that is fit to is including, but not limited to oleic acid, caproic acid, and enanthic acid (enthanic), sad, capric acid, isodecyl acid, n-nonanoic acid, LAURIC ACID 99 MIN, tetradecanoic acid; Palmitinic acid, linolic acid, linolenic acid, Triple Pressed Stearic Acid, Unimac 5680 ， docosoic, eicosanoic acid, arachidonic acid; Erucic acid, nonane diacid, Oleum Cocois, VT 18, Yatall MA, tallow, lard, neat's foot oil; Prunus amygdalus oil, wheatgerm oil, Semen Maydis oil, Oleum Gossypii semen, ricinoleate acid, ricinolic acid, rapeseed oil, palm kernel lipid acid; Sylvic acid, dimeracid, trimer acid, ozone acid, diacid, three acid and their mixture, and other acid in natural or synthetic source.What especially be fit to is oleic acid and sad and their mixture.In one embodiment, carboxylic acid and solvent merge such as amylalcohol and/or butanols.Carboxylic acid can be purchased at large.
This carboxylic acid with according to amine of the present invention, use together such as alkylamine or alkanolamine.The instance of the amine that is fit to comprises monoethanolamine, diethylolamine, trolamine, methylamine, n n dimetylaniline; Trimethylamine 99, ethamine, diethylamine, triethylamine, diethylethanolamine; Propylamine, isopropylamine, dipropylamine, diisopropylamine, tripropylamine; Triisopropylamine, or have 1 some other alkylamine or alkanolamines, perhaps ammonia, or their mixture to about 12 carbon atoms.That especially be fit to is dimethylethanolamine (" DMEA "); DMEA provides satisfactory stability property and good resistance to blistering.
According to the present invention, also use alcohol.Can use any alcohol compatible with this carboxylic acid.This alcohol can be branching or non-branching.In one embodiment, this alcohol have at least 4 carbon atoms and in another embodiment this alcohol have 5-7 carbon.If it is about 10 that carbon number is higher than, resistance to blistering can be impaired.Therefore, depend on user's needs, those skilled in the art can select suitable alcohol.
Silicoorganic compound and polymkeric substance are widely used in polymer composites such as plastics, rubber, tackiness agent, sealer, coating, printing ink because of its characteristic, its role is to improve macromolecular material use properties or processing characteristics.Silicone additives commonly used has silane coupling agent, silicone oil and silicone resin.Those skilled in the art can select voluntarily, and the present invention does not limit this.
Generally, carboxylic acid and amine, pure and mild organosilyl mol ratio are about 2.0 ~ 3.0:11.5 ~ 14:45 ~ 90:2 ~ 10, for example 2.5:12:60:8.
Additive of the present invention can specifically be applied to the coating of metal food jar.Term " food cans " is used to refer to the jar of the Foods or drinks that is used to hold any kind, the metal receptacle of container or any kind in this article.Typical metal comprises tin-coated steel, and tin-free steel, and blackplate are although the invention is not restricted to use these metals.
The invention further relates to and comprise film-forming resin, carboxylic acid, amine, pure and mild organosilyl water-based paint compositions.Any film-forming resin that is applicable to food cans can be used according to the invention.The instance that can be used for forming the polymkeric substance of resin comprises the PEMULEN TR2 of hydroxyl or carboxylic acid, and the polyester polymers of hydroxyl or carboxylic acid contains the polyether polyols with reduced unsaturation of isocyanic ester or hydroxyl and contains amine or the polyureas of isocyanic ester.These polymkeric substance further describe at US patent No.5, the 939,491, the 7th hurdle, and the 7th row is in the 8th hurdle the 2nd row; This patent and the patent of quoting are introduced for referencial use here.Particularly suitable film-forming resin is an epoxy acrylic resin, such as at US patent No.4, and those described in 212,781, it is for reference that this patent is introduced this paper.Can also use other epoxy acrylic resin.The solidifying agent of these resins also is described in ' 491 patents the 6th hurdle the 6th row in the 62nd row; Especially the linking agent that is fit to, especially the linking agent of epoxy acrylic resin comprises melamine and phenolic resin crosslinking agent." resol " be considered to be meant by one or more phenol monomers, such as phenol, and dihydroxyphenyl propane, the polymkeric substance of tert.-butyl phenol etc. and formolite reaction preparation.Can use the binding substances of solidifying agent.
Should be clear, coating of the present invention is liquid coating, more specifically says so water base or water-borne coatings.Because the reason of environment, water-borne coatings is more preferred than solvent based coating.It should be understood, however, that term as used herein " water-based " is meant, this coating mainly is water; Can comprise that the usual vehicle such as being lower than 20wt% (based on the gross weight of volatile matter) such as alcohol, and remains within the scope of the invention on a small quantity.In fact, the introducing of a spot of alcohol obviously is within the scope of the invention.
Noteworthy is that the present composition can also comprise pigment.Can use any suitable pigment, comprise TiO
2, ZnO and MgO.Add pigment in order to paint and to be used for hiding and the anti-high-sulfur food that contains, such as meat jar the pollution of coating.
Compsn of the present invention can also contain any other common additives such as tinting material, wax, lubricant, skimmer, wetting agent, softening agent, toughener and catalyzer.Any mineral acid or sulfonic acid catalyst can be used as catalyzer.What be particularly suitable for the food cans application is phosphoric acid and Witco 1298 Soft Acid.
Film-forming resin generally is present in the water-based paint compositions with the amount that is less than 16wt% to be higher than about 13wt%, and wherein wt% is that the gross weight in coating is a benchmark.This wt% is to be benchmark in total resin solid.Water or water/solvent mixture can be with 62 ~ 75wt%, and wherein wt% is that the gross weight in this coating is a benchmark.Carboxylic acid is present in the compsn with significant quantity.When being used for carboxylic acid, the amount of the carboxylic acid of the wetting ability of improvement coating when " significant quantity " is meant in joining coating.Wetting ability can be measured such as enamel paint rating test as herein described through mode known in the art.Very clear, various coating known in the art can contain trace carboxylic acid (that is,＜0.1wt%), this is owing to follow unintentional interpolation of various additives.Yet this amount is not used in improves the wetting of compsn, is not as used herein " significant quantity " therefore.Generally, the wt% of carboxylic acid is 0.5 ~ 4.0wt%, and wherein wt% also is to be benchmark in total resin solid, though in some formulation, can use even lower wt%.The wt% of amine generally is 18.5 ~ 21.5wt%, and such as 19-21, wherein wt% is to be benchmark in the total organic solvent.The wt% of alcohol can be 52 ~ 60wt%, and such as 52-58, wherein wt% is also with organic solvent, and gross weight is the benchmark meter.Pigment and other additive can account for the 11-15wt% of compsn, and such as 12 and 14wt%, wherein wt% is to be benchmark in total coating weight.
When using oleic acid simultaneously and when sad, oleic acid and sad mol ratio generally are 1.5 ~ 2.4: 1.5-7.Be surprisingly found out that sad use significantly increases the solids content of coating formulation.The amount of the acid of in this formulation, using as stated.
Carboxylic acid, amine and alcohol and organosilicon can be incorporated in the water-borne coatings in any suitable moment in the coating forming process.At first add amine, choose wantonly and add skimmer subsequently, add carboxylic acid and organosilicon then.Amine and carboxylic acid be premix not, so any amine salt of the carboxylic acid that possibly form is unintentionally.Carboxylic acid and amine are joined pigment wetting and the dispersion of pigment in coating that provides good in the pigment dispersion.If use the wetting and dispersed color of different modes, additive of the present invention can be used as the back additive and comprises in compsn.In either case, when being applied over metal base, this coating has the wetting of excellence.The attendant advantages of first method is that additive of the present invention helps to prepare coating through in pigment dispersion, adding.If there is not carboxylic acid of the present invention, then essential sand milling ground slurry, this compares cost with the inventive method higher and more consuming time.
The alkoxide component of additive of the present invention can be incorporated in the waterborne compositions through film-forming resin itself, if alcohol constitutes the part of the solvent that wherein contains resin.In addition, this alcohol can add separately in process for preparation at any time.
Except the excellent wettability of coating of the present invention, these coating also have the attendant advantages of environment coideal.More particularly, these coating have the low VOC that measures through the VOC installation that deducts water.
The VOC of coating of the present invention generally is less than or equal to about 2.0 pounds solvent per gallon (deducting water).
Except as otherwise specifically provided herein, all numeric ratios that this paper uses such as expression value, scope, amount or percentile those can be used as the front has word " approximately " to understand, even this term does not specially occur.Also have, all numerical ranges that this paper quotes are intended to comprise any subrange of wherein including in.The term " polymer " that this paper uses " be meant oligopolymer, homopolymer and multipolymer, and prefix " gather " be meant two or more.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical case of the present invention but non-restrictive example is following:
Embodiment 1
A kind of additive comprises: the carboxylic acid of significant quantity, amine, alcohol and organosilicon.
Wherein, carboxylic acid, amine, pure and mild organosilyl mol ratio are 2.0:14:45:10.
The coating composition that is added with above-mentioned additive is: the carboxylic acid of film-forming resin, significant quantity, amine, alcohol and organosilicon.
Embodiment 2
A kind of additive comprises: the carboxylic acid of significant quantity, amine, alcohol and organosilicon.
Wherein, carboxylic acid, amine, pure and mild organosilyl mol ratio are 3.0:11.5:90:2.
The coating composition that is added with above-mentioned additive is: the carboxylic acid of film-forming resin, significant quantity, amine, alcohol and organosilicon.
Embodiment 3
A kind of additive comprises: the carboxylic acid of significant quantity, amine, alcohol and organosilicon.
Wherein, carboxylic acid, amine, pure and mild organosilyl mol ratio are 2.5:13:59:6.
The coating composition that is added with above-mentioned additive is: the carboxylic acid of film-forming resin, significant quantity, amine, alcohol and organosilicon.
Comparative Examples
A kind of additive comprises: the carboxylic acid of significant quantity, amine, alcohol.
Wherein, the mol ratio of carboxylic acid, amine, alcohol is 2.5:13:59.
The coating composition that is added with above-mentioned additive is: the carboxylic acid of film-forming resin, significant quantity, amine, alcohol.
VOC to the foregoing description 1-3 coating detects, and the VOC that obtains this coating all about 2.0lb/gal (deducting water), compares at 3.5b/gal (deducting water) with the VOC of the said coating of Comparative Examples, has very big progress.This coating can spray under the high-pressure airless condition, and is excellent wetting to obtain on tin-coated steel, to have, the uniform thin film of low enamel paint grading and the good performance in vegetable food is packed.
Should be noted that and understand, under the situation that does not break away from the desired the spirit and scope of the present invention of accompanying Claim, can make various modifications and improvement the present invention of above-mentioned detailed description.Therefore, the scope of the technical scheme of requirement protection does not receive the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention explains detailed method of the present invention through the foregoing description, but the present invention is not limited to above-mentioned detailed method, does not mean that promptly the present invention must rely on above-mentioned detailed method and could implement.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. additive is characterized in that it comprises:
A) carboxylic acid;
B) amine;
C) alcohol; With
D) organosilicon;
Wherein the mol ratio of a: b: c:d is 2.0 ~ 3.0:11.5 ~ 14:45 ~ 90:2 ~ 10.
2. the additive of claim 1 is characterized in that, said carboxylic acid has 2-18 carbon atom, preferred 8-18 carbon atom, further preferred 10 ~ 15 carbon atoms;
Preferably, said carboxylic acid is that oleic acid is or/and sad.
3. the described additive of one of claim 1-2 is characterized in that, said amine is dimethylethanolamine;
Preferably, said alcohol has 4 carbon atoms at least, preferred 4-10 carbon, further preferred 4 ~ 7 carbon, more preferably amylalcohols.
4. a water-based paint compositions is characterized in that, said coating composition comprises:
A) film-forming resin;
B) carboxylic acid of significant quantity;
C) amine;
D) alcohol; With
E) organosilicon.
5. compsn as claimed in claim 4; It is characterized in that said film-forming resin is selected from the mixture of a kind of in polyvinyl acetate emulsion, Z 150PH emulsion, ethene-vinyl acetate copolymer emulsion, styrene-propene acid, vinylformic acid-methylacrylic acid, the tertiary carbon acid esters-vinyl acetate between to for plastic acrylic resin or at least two kinds.
6. like claim 4 or 5 described compsns, it is characterized in that said carboxylic acid has 2-18 carbon atom, preferred 8-18 carbon atom, further preferred 10 ~ 15 carbon atoms.
7. like the described compsn of one of claim 4-6, it is characterized in that said carboxylic acid is that oleic acid is or/and sad.
8. like the described compsn of one of claim 4-7, it is characterized in that said amine is dimethylethanolamine.
9. like the described compsn of one of claim 4-8, it is characterized in that said alcohol has 4 carbon atoms at least, preferred 4-10 carbon, further preferred 4 ~ 7 carbon, more preferably amylalcohols.
10. like the described compsn of one of claim 4-9, said compsn also comprises pigment;
Preferably, said pigment is titanium oxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101800217A CN102702835A (en) | 2012-06-01 | 2012-06-01 | Low-VOC (Volatile Organic Compound) water-based coating additive |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101800217A CN102702835A (en) | 2012-06-01 | 2012-06-01 | Low-VOC (Volatile Organic Compound) water-based coating additive |
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| CN2012101800217A Pending CN102702835A (en) | 2012-06-01 | 2012-06-01 | Low-VOC (Volatile Organic Compound) water-based coating additive |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5939491A (en) * | 1997-08-01 | 1999-08-17 | Ppg Industries Ohio, Inc. | Curable compositions based on functional polysiloxanes |
| CN1703470A (en) * | 2002-11-05 | 2005-11-30 | Ppg工业俄亥俄公司 | Additives for low voc aqueous coatings |
| CN101410438A (en) * | 2006-01-27 | 2009-04-15 | 莫门蒂夫性能材料股份有限公司 | Low VOC epoxy silane oligomer and compositions containing same |
-
2012
- 2012-06-01 CN CN2012101800217A patent/CN102702835A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5939491A (en) * | 1997-08-01 | 1999-08-17 | Ppg Industries Ohio, Inc. | Curable compositions based on functional polysiloxanes |
| CN1703470A (en) * | 2002-11-05 | 2005-11-30 | Ppg工业俄亥俄公司 | Additives for low voc aqueous coatings |
| CN101410438A (en) * | 2006-01-27 | 2009-04-15 | 莫门蒂夫性能材料股份有限公司 | Low VOC epoxy silane oligomer and compositions containing same |
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Application publication date: 20121003 |